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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Nickel-Catalyzed Cross-Electrophile Coupling of Alkynyl Halides With Allylic Acetates
Quan Lin1, Liping Lin1, Yuying Wang1
1College of Chemistry and Materials Science, Gannan Normal University, Ganzhou, P. R. China.
Abstract:
We have developed a Ni-catalyzed cross-electrophile coupling (XEC) strategy that enables the efficient synthesis of diverse skipped enynes from readily accessible alkynyl halides and allylic acetates. This method exhibits broad substrate scope, accommodating a wide range of aliphatic and aromatic electrophiles, as well as complex natural product- and pharmaceutical-derived motifs, which remains a challenge using the current methods. Mechanistic experiments and DFT studies support a double oxidative addition pathway, wherein Ni0 preferentially undergoes oxidative addition with the alkynyl halide. To our knowledge, this work represents the first example of a TM-catalyzed reductive cross-coupling between two electrophiles for the preparation of skipped enynes. The process proceeds with excellent stereoselectivity and notable regioselectivity, offering a promising platform for future development of asymmetric skipped enynes synthesis.
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